Enantioselective Intramolecular CH-Insertions upon Cu-Catalyzed Decomposition of Phenyliodonium Ylides.docVIP

Molecules 2001, 6, 258-266 molecules ISSN 1420-3049 Enantioselective Intramolecular CH-Insertions upon Cu- Catalyzed Decomposition of Phenyliodonium Ylides. ? Paul Müller*, Christelle Boléa Department of Organic Chemistry, University of Geneva 30, Quai Ernest-Ansermet, CH-1211 Geneva 4, Switzerland. Tel: +41 22 702 6527, Fax: +41 22 328 7396. ? This paper was at the Fourth Electronic Conference on Synthetic Organic Chemistry (ECSOC-4), September 1-30, 2000. Paper A0015. * Author to whom correspondence should be addressed; e-mail: paul.muller@chiorg.unige.ch Received: 24 January 2001/ Accepted: 7 February 2001 / Published: 28 February 2001 Abstract: The Cu-catalyzed intramolecular CH insertion of phenyliodonium ylide 5b has been investigated at 0° C in the presence of several chiral ligands. Enantioselectivities vary in the range of 38–72 %, and are higher than those resulting from reaction of the diazo compound 5c at 65° C. The results are consistent with a carbenoid mechanism for Cu-catalyzed decomposition of phenyliodonium ylides. Keywords: Phenyliodonium ylides, CH insertion, Cu-catalysis, asymmetric induction. Introduction Phenyliodonium ylides are of interest as substitutes for diazo compounds in transition metal- catalyzed carbenoid reactions. Their decomposition under photochemical [1,2] or thermal conditions [1,3], or in the presence of transition metal catalysts [2-4] affords products typical for carbene or metal carbenoid intermediates. However, the experimental evidence supporting these mechanistic hypotheses is scarce. The intermediacy of metal carbenoids upon diazo decomposition by transition metal-catalysts is well established. These reactions proceed with almost perfect enantioselectivity with the appropriate chiral, non-racemic catalysts [5]. In contrast, the mechanism of the transition metal-catalyzed decomposition of phenyliodonium ylides is c